We found that the alignments of the alkali cations can be controlled by a distortion of Prussian blue framework; the rubidium ions form a rod structure in a distorted framework of Rb0.85Cu[Fe(CN)6]0.95·1.3H2O, while the cesium ions are isolated dot structures in a non-distorted framework of Cs0.97Cu[Fe(CN)6]0.99·1.1H2O. The Madelung energy calculations revealed that the novel rod structure is stabilized by the alternating rotations of the [Fe(CN)6] units within the three-dimensional coordination polymer framework.